The synthesis of indolo- and pyrrolo[2,1-a]isoquinolines

The synthesis of fused isoquinolines from N-benzyl protected indoles and pyrroles is described. For example, treatment of t-butyl-2-(2-formyl-3,4-dihydro-1-naphthalenyl)-3-methyl-1H-indole-1-carboxylate with KOBu^t in DMF provided 14-methyl-8-phenylbenzo[h]indolo[2,1-a]isoquinoline in good yield. Analogous N-benzylpyrrole precursors could similarly be cyclized to give pyrrolo[2,1-a]isoquinolines.     

The di-t-butylsilylene protecting group as a bridging unit in linear and macrocyclic bis-malonates for the regioselective multifunctionalization of C60

Fullerene equatorial bis-adducts have been prepared with high regioselectivity by a double Bingel reaction between [60]fullerene and di-t-butylsilylene-tethered bis-malonates. Macrocyclic bis-malonates incorporating di-t-butylsilylene moieties have also been prepared and used to functionalize C₆₀ in multiple Bingel cyclopropanations. Fullerene bis-adducts with a cis-2 addition pattern and tris-adducts with an e,e,e addition pattern have been thus obtained. Finally, the bridging di-t-butylsilylene is not only a directing group for the cyclization step, it is also a protecting group that can be readily cleaved to afford the corresponding acyclic fullerene polyols.     

Base- and light-assisted synthesis of anthracenes from 3-allylnaphthalene-2-carbaldehydes

The synthesis of substituted anthracenes from naphthalene precursors is described. The key step involved heating ortho-allyl substituted naphthalene-2-carbaldehydes and potassium t-butoxide in DMF with concomitant irradiation from a high pressure mercury lamp to afford anthracenes in yields of 76-98%.     

Micellization behavior of diblock and triblock copolymers of poly(t-butyl methacrylate) bearing associating short polystyrene end-blocks

Anionic polymerization high vacuum techniques were employed for the synthesis of a diblock (PS-b-PtBuMA) and two triblock (PS-b-PtBuMA-b-PS) copolymers of polystyrene (PS) and poly(t-butyl methacrylate) (PtBuMA) bearing similar low molecular weight PS end-block(s). Dilute solution viscometry, as well as static and dynamic light scattering, were employed to assess whether the short PS end-blocks were able to promote association in t-amyl alcohol, a selective solvent for PtBuMA. The effect of macromolecular architecture on the association behavior of the copolymers was also examined.     

A simple route to β-aminomethylketones

A simple procedure leading to β-aminomethylketones has been developed. The procedure involves base-catalyzed Michael-type addition of sodium t-butyl acetoacetate to N-Boc imines generated in situ followed by hydrolysis and decarboxylation of the adducts.     

A concise synthesis of novel naphtho[a]carbazoles and benzo[c]carbazoles

Starting from simple indole precursors the synthesis of naphtho[a]carbazoles and benzo[c]carbazoles is described. Key steps include the use of the Suzuki-Miyaura reaction to afford 2- or 3-aryl substituted indoles, as well as a potassium t-butoxide and light assisted aromatic ring-forming reaction.     

Limits of detection and decision. Part 2

Extensive Monte Carlo studies of instrumental limits of detection (LODs) were performed on a simple univariate chemical measurement system having homoscedastic, Gaussian measurement noise and using ordinary least squares (OLS) processing of tens of millions of independent calibration curve data sets. It was found that experimental decision and detection limits in the content domain were distributed as scaled reciprocals of noncentral t variates. In the response domain, the decision and detection limits were distributed as scaled χ variates. Rates of false negatives were found to be as expected statistically and no bias was found. However, use of detection limit expressions based on critical values of the noncentrality parameter of the noncentral t distribution were found to be significantly biased, resulting in substantial bias in rates of false negatives.     

Unexpected conversion of alkyl azides to alkyl iodides and of aryl azides to N-tert-butyl anilines

In the presence of tert-butyl iodide, alkyl azides are converted into the corresponding iodides at room temperature, whereas, N-t-Bu anilines are obtained from aryl azides under the same experimental conditions. A mechanism is proposed to explain this unusual reactivity.     

Polyfluorinated arylnitrosamines

N-Methyl-, N-n-butyl-, N-t-butylperfluoroarylamines undergo nitrosation with nitrous acid to give the corresponding N-nitroso derivatives. Perfluoroaryl groups were selected from the benzene, indane, biphenyl, naphthalene and pyridine series. According to ¹H and ¹⁹F NMR spectra, N-nitroso-N-methyl derivatives of polyfluoroarenes consist of E and Z isomers with the former prevailing. The more bulky n-butyl group promotes an increase in the formation of Z isomers. Only Z isomers have been obtained from N-t-butyl derivatives of perfluorinated 4-toluidine and 4-aminopyridine. The structure of the Z isomer of N-nitroso-N-methylperfluoro-4-toluidine is confirmed by X-ray data.     

Selective N-debenzylation of amides with p-TsOH

N-Benzylamides were debenzylated efficiently with 4 equiv. of p-TsOH in refluxing toluene. Good to quantitative yields of the desired primary amides were obtained within 2-4 h from a wide variety of N-2,4-dimethoxybenzylamides. N-4-Methoxylbenzyl amides and N-benzylamides were also debenzylated cleanly. In the case of N-2,4-dimethoxylbenzylamides, selective N-debenzylation was possible in the presence of N-Fmoc, N-t-BOC or N-trityl-protection. Protected amino acid amides survived these conditions without any detectable epimerization.     

Bi2O3 catalyzed asymmetric oxidation of sulfides

Bismuth based catalytic system for the asymmetric oxidation of alkyl and aryl benzyl sulfides using t-BuOOH as the oxidant has been investigated. This method affords sulfoxides with high enantioselectivities (up to 98% ee) and good yields in reasonable time. The over oxidized product namely the sulfone was not observed. The described method has wide range of applications, exhibits chemoselectivity/enantioselectivity, and proceeds under mild and environmentally friendly reaction conditions.     

Cu(II)-catalyzed oxidation of sulfides

A variety of sulfides and disulfides were converted into the corresponding sulfoxide derivatives with 70% t-BuOOH (water) as the oxidant in the presence of catalytic quantity of CuBr₂. The method described does not involve cumbersome work-up, has wide range of applicabilities, exhibits chemoselectivity, and proceeds under mild reaction conditions, and the resulting products are obtained in good yields within reasonable time.     

RuCl3-TBHP mediated allylic oxidation of Δ lanosterol derivatives

A variety of Δ⁸⁽⁹⁾-lanosterol derivatives were converted into 7,11-dienones using t-butyl hydroperoxide in the presence of ruthenium chloride (RuCl₃) in good yields.     

The effect that 6-tert-butoxyhexyl functionalization has on ethylene polymerization in ansa-zirconocene dichlorides

Ethylene polymerization studies have been carried out with novel precatalysts of the type: [(η⁵-C₁₃H₈)-X(t-BuOC₆H₁₂)Me-(η⁵-C₅H₄)]ZrCl₂ [X=C [1a], Si [2a]], [(η⁵-C₁₃H₈)-XMe₂-(η⁵-(t-BuOC₆H₁₂C₅H₃))] ZrCl₂ [X=C [3a], Si [4a]] in the presence of excess methylalumoxane (MAO) to compare their catalytic activity and to delineate the effect of the 6-t-butoxyhexyl functionality on ethylene polymerization. The precatalysts [1a] and [2a] with the bridge functionality showed higher activity in ethylene polymerization than the corresponding complexes [3a] and [4a] which have it on the Cp ring moiety. On the other hand the silyl bridged complexes [2a] and [4a] produced a higher molecular weight polyethylene than the carbon-bridged one, regardless of the location of functional group.     

Direct synthesis of hetero-biaryl compounds containing an unprotected NH2 group via Suzuki-Miyaura reaction

Hetero-biaryl compounds were prepared via the Suzuki-Miyaura coupling reaction of hetero-aryl moieties containing an unprotected NH₂ group and arylboronic acids. D-t-BPF was found to be an efficient ligand for the cross-coupling of NH₂-unprotected hetero-aryl chlorides with phenylboronic acid.     

Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands

Elimination of methane during thermolysis of title compounds results in the formation of σ-Ti-C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(η⁵-C₅Me₄t-Bu)₂] (5) eliminates methane at 110 °C to give cleanly [Ti(III)(η⁵:η¹-C₅Me₄CMe₂CH₂)(η⁵-C₅Me₄t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(η⁵-C₅Me₄CH₂Ph)₂] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(η⁵:η¹-C₅Me₄CH₂-o-C₆H₄)(η⁵-C₅Me₄CH₂Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe₂{η⁵-C₅Me₄t-Bu)}₂] (9) eliminates two methane molecules at 110 °C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{η⁵:η¹:η¹-C₅Me₃(CH₂)(CMe₂CH₂)}(η⁵-C₅Me₄t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe₂(η⁵-C₅Me₄CH₂Ph)₂] (10) eliminates at 110 °C only one methane molecule to afford [TiMe(η⁵:η¹-C₅Me₄CH₂-o-C₆H₄)(η⁵-C₅Me₄CH₂Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 °C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined.     

Comparison of supercritical fluid and Soxhlet extractions for the quantification of hydrocarbons from Euphorbia macroclada

This study compares conventional Soxhlet extraction and analytical scale supercritical fluid extraction (SFE) for their yields in extracting of hydrocarbons from arid-land plant Euphorbia macroclada. The plant material was firstly sequentially extracted with supercritical carbon dioxide, modified with 10% methanol (v/v) in the optimum conditions that is a pressure of 400 atm and a temperature of 50 °C and then it was sonicated in methylene chloride for an additional 4 h. E. macroclada was secondly extracted by using a Soxhlet apparatus at 30 °C for 8 h in methylene chloride. The validated SFE was then compared to the extraction yield of E. macroclada with a Soxhlet extraction by using the Student’s t-test at the 95% confidence level. All of extracts were fractionated with silica-gel in a glass column to get better hydrocarbon yields. Thus, the highest hydrocarbons yield from E. macroclada was achieved with SFE (5.8%) when it compared with Soxhlet extractions (1.1%). Gas chromatography (GC) analysis was performed to determine the quantitative hydrocarbons from plant material. The greatest quantitative hydrocarbon recovery from GC was obtained by supercritical carbon dioxide extract (0.6 mg g⁻¹).     

Base promoted facile route to functionalized benzo[b][1,8]naphthyridin-2-(1H)-ones from N-benzyl-N-(3-cyanoquinolin-2-yl)acetamides

A facile synthesis of 4-amino-N-benzylbenzo[b][1,8]naphthyridin-2(1H)-ones 3 is described from N-benzyl-N-(3-cyanoquinolin-2-yl)acetamides 2 with t-BuOK in excellent yields in mild conditions. These reactions proceeded at room temperature under aerobic atmosphere in very short period. The cyclization reactions were also extended with N-alkyl amino acetamide analogues affording the products in good yields.     

A novel and efficient amidation of 2-aminothiazole

A facile and efficient method has been developed for the synthesis of novel thiazolyl carboxamide derivatives by direct reaction of the corresponding esters and 2-aminothiazole. Treatment of 2-aminothiozole with various carboxylic esters in the presence of t-butylmagnesium chloride provides the biologically significant thiazolyl carboxamide derivatives in good to excellent yields.     

Syntheses and structures of zinc and tin(II) compounds with hemilabile N-silyl-tert-butylamido and N-silyl-p-tolylamido ligands that contain pendent tert-butoxy groups

Syntheses and solid-state structures of zinc and tin(II) compounds, containing the N-silyl-amide ligands (O^tBu)(NR)SiMe₂, R = ^tBu (L^tBu), or R = p-tolyl (L^pTol), are reported. The N-silyl amines were synthesized by modified published procedures from commercially available Me₂SiCl₂, ^tBuOH, and ^tBuNH₂, or p-Me-C₆H₄NH₂, respectively. Treatment of SnCl₂ with LiL^pTol furnished Sn(L^pTol)₂, which was X-ray structurally characterized and shown to contain two covalent Sn-N bonds and two asymmetrical O → Sn donor bonds. The single-crystal X-ray structure of Sn(L^tBu)₂ revealed a much more symmetrically-coordinated, pseudo-trigonal-bipyramidal tin atom. Aminolysis of diethylzinc with HL^pTol produced [EtZn(L^pTol)]₂, which crystallized as a centrosymmetric dimer, containing four-coordinate zinc atoms connected by bridging amides. Zinc dichloride, by contrast, reacted with two equivalents of LiL^tBu to produce the homoleptic, pseudo-spirocyclic Zn(L^tBu)₂.